It is not possible to encode ASCII in Big5.
Big5 is purely a double-byte character set. To allow intermixing of single-byte character sets, all Big5 2-byte character encodings have the high-order bit set. The standard never specified WHICH SBCS was to be used, and the de-facto standard is ASCII, which can unambiguously be distinguished because all ASCII characters have the high-order bit clear.
Put another way, Big5 contains no 2-byte encodings corresponding to the standard ASCII character set, so the only way to include an XML prologue and tag delimiters is to use ASCII characters.